CN113299905A - Preparation method of single crystal nickel cobalt lithium manganate ternary material - Google Patents
Preparation method of single crystal nickel cobalt lithium manganate ternary material Download PDFInfo
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- CN113299905A CN113299905A CN202110557304.8A CN202110557304A CN113299905A CN 113299905 A CN113299905 A CN 113299905A CN 202110557304 A CN202110557304 A CN 202110557304A CN 113299905 A CN113299905 A CN 113299905A
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- 239000013078 crystal Substances 0.000 title claims abstract description 140
- 239000000463 material Substances 0.000 title claims abstract description 74
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 61
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 26
- 239000002245 particle Substances 0.000 abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000011164 primary particle Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 18
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
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- 229910003002 lithium salt Inorganic materials 0.000 description 4
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
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- 238000004904 shortening Methods 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
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- 238000007873 sieving Methods 0.000 description 2
- 238000010947 wet-dispersion method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- 229910003684 NixCoyMnz Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a preparation method of a single crystal nickel cobalt lithium manganate ternary material. The method comprises the following steps: (1) mixing a ternary 523 single crystal precursor, a lithium source and a nano fluxing agent containing doping elements, controlling the weight ratio of the lithium source to the ternary 523 single crystal precursor to be (0.5-1):1, and then calcining to obtain an aggregate structure seed crystal with D50 of 6-9 mu m; (2) and (2) mixing the aggregate structure seed crystal obtained in the step (1) with a ternary 523 single crystal precursor and a lithium source to obtain a mixture, and then calcining the mixture to obtain the single crystal nickel cobalt lithium manganate ternary material. The method can obtain the ternary material with good single crystal form, round and smooth particles and good primary particle size consistency, has the advantages of high capacity, high first coulombic efficiency and good cycle performance, has the advantages of low sintering temperature, short sintering period and simple preparation process in the whole preparation process, and has higher commercial value.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a single crystal nickel cobalt lithium manganate ternary material.
Background
The nickel cobalt lithium manganate material, namely a ternary material, combines the advantages of the three materials through the synergistic effect of Ni-Co-Mn: LiCoO2Good rate capability of LiNiO2High specific capacity and LiMnO2The lithium ion battery has high safety and low cost, and the like, and is one of the most promising novel lithium ion battery positive electrode materials.
The preparation method of the introduced crystal seed is common in the production process of the ternary precursor, and belongs to liquid phase reaction. For example, patent application CN202010109284.3 discloses a method for preparing a high-sphericity ternary precursor seed crystal and a method for preparing a high-sphericity ternary precursor using the seed crystal. The method leads the produced high-sphericity seed crystal to grow gradually by introducing the seed crystal with high sphericity and controlling the reaction conditions, thereby obtaining the precursor with high sphericity and meeting the required grain diameter and shortening the production period. However, for the preparation process of the ternary material, which belongs to the solid-phase sintering reaction, cases of shortening the production period of the ternary material and obtaining a material with excellent electrochemical performance by a method of introducing a seed crystal are rare and have not been verified much. Patent application CN201711481964.2 discloses a lithium ion battery anode material, a preparation method and application thereof, wherein the anode material contains elements shown in a chemical formula I, is doped with M elements and is coated with N elements; the first chemical formula is as follows: livNixCoyMnzO2Wherein v is more than or equal to 1.00 and less than or equal to 1.10; x is more than or equal to 0.30 and less than or equal to 0.70; y is more than or equal to 0.05 and less than or equal to 0.40; z is more than or equal to 0.20 and less than or equal to 0.50, and 2x +4y +4z is 2.5-3.5; the M element is selected from one or more than two of aluminum, magnesium, titanium or zirconium; the N element is selected from one or more than two of cobalt, lanthanum or yttrium. The patent application changes the ternary material by means of doping and claddingAnd (5) sexual treatment. However, during the doping and coating operation, a wet mixing mode is adopted, and deionized water is used as a dispersing agent. After the deionized water is used for wet dispersion in the doping process, drying is carried out at 200 ℃, heat preservation is carried out for 1h, and a drying procedure is additionally added, so that the process flow is complicated, the process control points are increased, and the energy consumption is increased. In the coating process, deionized water is also used for wet dispersion, but drying treatment is not carried out, the mixture is directly fed into a furnace for sintering, the mixture with high water content is directly fed into the furnace for sintering without drying treatment, a large amount of volatile water can damage the electronic component structure of the sintering furnace, and the service life of the sintering furnace is seriously shortened.
Patent application CN201911144733.1 discloses a single crystal type nickel cobalt lithium manganate ternary cathode material and a low-temperature sintering preparation method thereof. The method comprises the steps of taking lithium salt and an NCM ternary precursor with the D50 content of 2.5-5.5 um as raw materials, uniformly mixing the raw materials in a dry mixing mode, and carrying out primary sintering at the sintering temperature of 870-920 ℃; sequentially carrying out primary crushing and primary screening on the product obtained after the primary sintering to obtain a primary sintered base material; mixing the primary sintered base material with a nano coating agent, performing secondary sintering, crushing and secondary sieving in sequence to obtain a product; in the mixture of the NCM ternary precursor and the lithium salt, the molar ratio of Li/(Ni + Co + Mn) is 1.02-1.2, and the nano coating agent is one or a mixture of oxides and hydroxides containing metal elements. The method realizes low-temperature sintering of the single-crystal nickel cobalt lithium manganate ternary positive electrode material, improves the structural stability of the material, and further improves the electrochemical cycle performance. However, the patent application modifies the ternary material by doping and coating means, the first sintering is carried out at a relatively low sintering temperature, the heat preservation time is 8-20 h, the first sintering heat preservation time is 12h in all embodiments, the sintering period is long, only the maximum sintering temperature and the heat preservation time of the maximum sintering temperature are described in the patent application, and a complete sintering curve is not indicated. In addition, the patent application proposes that the Li/Me ratio in the raw materials is improved, the sintering driving force is reduced, and the mode which is beneficial to the solid-phase sintering reaction of the lithium source and the ternary precursor belongs to a conventional means and can be easily obtained through simple experiments.
Patent application CN201910767039.9 discloses a method for preparing a nickel cobalt lithium manganate single crystal ternary material, which comprises the following steps of (1) mixing a precursor (Ni 0.5Co 0.2Mn 0.3) OH with battery-grade lithium carbonate, and adding a zirconium compound to ensure that the mass content of zirconium in the obtained mixture is 0.1-0.25% of the total mass of the mixture; (2) carrying out dry mixing on the mixture obtained in the step (1); (3) roasting the mixture obtained in the step (2) to obtain a material block; (4) sequentially carrying out rotary wheel grinding, jet milling and sieving on the material blocks obtained in the step (3); wherein the average particle size D50 of the battery grade lithium carbonate is 10-12 μm. The method has simple preparation process and is easy for industrial production and application; the obtained nickel cobalt lithium manganate single crystal ternary material has excellent electrochemical performance, stable material performance and good cycle performance. However, the method has the advantages of higher sintering temperature, longer heat preservation time, high energy consumption and longer preparation period.
Patent application CN201910729397 discloses a preparation process of a micron-sized single-crystal primary-particle ternary cathode material, wherein nickel salt, cobalt salt and manganese salt solution are mixed according to the proportion of x, y, z, ammonia water serving as a complexing agent is added, sodium hydroxide serving as a precipitator is added, the mixing temperature is 50-90 ℃, the pH value is 11-13, a coprecipitate is obtained after mixing, and solid-liquid separation is carried out on the coprecipitate by adopting a centrifugal machine to obtain a precursor A; adding lithium salt into the precursor A, uniformly mixing in a high-speed mixer, and carrying out heat treatment to obtain 0.1-1 mu m seed crystal small single crystal particles B; and adding the seed crystal small single crystal particles B into the precursor A, wherein the mixing weight ratio of the small single crystal particles B to the precursor A is 1:25-1:10, and simultaneously mixing the seed crystal small single crystal particles B and the precursor A with lithium salt for solid phase reaction to obtain single crystal particles with the particle size of more than 4 microns. However, the single crystal particles obtained by the preparation method are large, the primary particle size is more than 4 μm, and the larger the single crystal particle size is, the larger the impedance is, the smaller the lithium ion diffusion coefficient of the material is, which is not favorable for the exertion of the material capacity.
Disclosure of Invention
The invention aims to solve the problems of poor primary particle size consistency, low capacity, low first coulombic efficiency, poor cycle performance, high sintering temperature in the preparation process, complex preparation process and the like of a ternary cathode material in the prior art, and provides a preparation method of a single-crystal nickel cobalt lithium manganate ternary material.
In order to achieve the purpose, the invention provides a preparation method of a single-crystal nickel cobalt lithium manganate ternary material, which comprises the following steps:
(1) mixing a ternary 523 single crystal precursor, a lithium source and a nano fluxing agent containing doping elements, controlling the weight ratio of the lithium source to the ternary 523 single crystal precursor to be (0.5-1):1, and then calcining to obtain an aggregate structure seed crystal with D50 of 6-9 mu m;
(2) mixing the aggregate structure seed crystal obtained in the step (1) with a ternary 523 single crystal precursor and a lithium source to obtain a mixture, and then calcining the mixture to obtain a single crystal nickel cobalt lithium manganate ternary material;
wherein the chemical formula of the ternary 523 single crystal precursor is Ni0.5Co0.2Mn0.3(OH)2；
In the step (1), the doping element is selected from at least one of Zr, Ti, Mg, Al and B; the weight of the doping element is 0.1-0.35% of the weight of the ternary 523 single crystal precursor;
in the step (2), the ratio of the quantity of the substance of the lithium element in the lithium source to the total quantity of the three elements of nickel, cobalt and manganese in the ternary 523 single-crystal precursor is (0.9-1.02): 1; the mixture contains 10-20 wt% of agglomerate structure seed crystal.
Preferably, the lithium source is lithium carbonate.
Preferably, in step (1), the calcination conditions include: the heating rate is 2-5 ℃/min, the calcination temperature is 600-800 ℃, and the calcination time is 18-24 h.
Preferably, in step (1), the atmosphere of the calcination is air.
Preferably, in step (1), the nano-flux is a mixture of one or more of oxides, fluorides, hydroxides, carbonates and basic carbonates containing doping elements.
Preferably, in step (2), the specific process of the calcination is: the temperature is raised to 700-800 ℃ at the rate of 1-5 ℃/min for calcining for 2-4h, and the temperature is raised to 920-940 ℃ at the rate of 1-4 ℃/min for calcining for 6-10 h.
Preferably, in step (1), the mixing is carried out in a VC mixer.
Preferably, in step (2), the mixing is carried out in a high-speed mixer.
Preferably, in step (2), the atmosphere of the calcination is air.
Preferably, in steps (1) and (2), the calcination is carried out in a muffle furnace.
According to the method, the aggregate structure large-particle seed crystal with D50 of 6-9 microns and specific doping elements is prepared in advance, the seed crystal initially has the layered structure characteristic of nickel cobalt lithium manganate, then a precursor, a lithium source and the seed crystal are added in a material mixing stage, and a ternary material with good single crystal form, round particles and good primary particle size consistency is obtained through sintering.
Drawings
FIG. 1 is an SEM image of seed crystals of the agglomerate structure made in example 1;
FIG. 2 is an SEM image of the seed crystal of the agglomerate structure made in example 2;
FIG. 3 is an SEM image of the seed crystal of the agglomerate structure made in example 3;
FIG. 4 is an SEM image of the seed crystal of the agglomerate structure made in example 4;
FIG. 5 is a graph representing particle size of the agglomerate structure seed obtained in example 1;
FIG. 6 is an XRD pattern of the agglomerate structure seed obtained in example 1;
FIG. 7 is an SEM image of a ternary material made in example 1;
FIG. 8 is an SEM image of a ternary material made in example 2;
FIG. 9 is an SEM image of a ternary material made in example 3;
FIG. 10 is an SEM image of a ternary material made in example 4;
FIG. 11 is an SEM image of the ternary material made in comparative example 1;
FIG. 12 is a graph comparing the specific discharge capacity at 1C50 cycles of discharge for example 1 and comparative example 1.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a single crystal nickel cobalt lithium manganate ternary material, which comprises the following steps:
(1) mixing a ternary 523 single crystal precursor, a lithium source and a nano fluxing agent containing doping elements, controlling the weight ratio of the lithium source to the ternary 523 single crystal precursor to be (0.5-1):1, and then calcining to obtain an aggregate structure seed crystal with D50 of 6-9 mu m;
(2) mixing the aggregate structure seed crystal obtained in the step (1) with a ternary 523 single crystal precursor and a lithium source to obtain a mixture, and then calcining the mixture to obtain a single crystal nickel cobalt lithium manganate ternary material;
wherein the chemical formula of the ternary 523 single crystal precursor is Ni0.5Co0.2Mn0.3(OH)2；
In the step (1), the doping element is selected from at least one of Zr, Ti, Mg, Al and B; the weight of the doping element is 0.1-0.35% of the weight of the ternary 523 single crystal precursor;
in the step (2), the ratio of the quantity of the substance of the lithium element in the lithium source to the total quantity of the three elements of nickel, cobalt and manganese in the ternary 523 single-crystal precursor is (0.9-1.02): 1; the mixture contains 10-20 wt% of agglomerate structure seed crystal.
In the present invention, in step (1), the weight ratio of the lithium source to the ternary 523 single crystal precursor may be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1: 1.
In the present invention, in the step (1), the weight of the doping element may be 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, or 0.35 wt% of the weight of the ternary 523 single crystal precursor.
In a preferred embodiment, the lithium source is lithium carbonate.
In a preferred embodiment, in step (1), the conditions of the calcination include: the heating rate is 2-5 ℃/min, the calcination temperature is 600-800 ℃, and the calcination time is 18-24 h. Specifically, the heating rate can be 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min; the calcination temperature may be 600 deg.C, 620 deg.C, 640 deg.C, 650 deg.C, 660 deg.C, 680 deg.C, 700 deg.C, 720 deg.C, 740 deg.C, 750 deg.C, 760 deg.C, 780 deg.C or 800 deg.C; the calcination time may be 18h, 19h, 20h, 21h, 22h, 23h, or 24 h.
In a preferred embodiment, in step (1), the atmosphere of the calcination is air.
In a preferred embodiment, in step (1), the nano-flux is a mixture of one or more of oxides, fluorides, hydroxides, carbonates and basic carbonates containing doping elements.
In the present invention, in step (2), the ratio of the amount of the substance of the lithium element in the lithium source to the total amount of the three elements of nickel, cobalt and manganese in the ternary 523 single crystal precursor may be 0.9:1, 0.92:1, 0.94:1, 0.96:1, 0.98:1, 1.00:1, or 1.02: 1.
In the present invention, in the step (2), the content of the agglomerate structure seeds in the mixture may be 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%.
In a preferred embodiment, in step (2), the calcination is performed by the following specific process: heating to 700-800 ℃ at the heating rate of 1-5 ℃/min and calcining for 2-4 h; specifically, the heating rate can be 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min, the calcining temperature can be 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃ or 800 ℃, and the calcining time can be 2h, 2.5h, 3h, 3.5h or 4 h; the temperature is raised to 920-940 ℃ at the heating rate of 1-4 ℃/min for calcining for 6-10 h. Specifically, the heating rate can be 1 ℃/min, 2 ℃/min, 3 ℃/min or 4 ℃/min, the calcining temperature can be 920 ℃, 925 ℃, 930 ℃, 935 ℃ or 940 ℃, and the calcining time can be 6h, 7h, 8h, 9h or 10 h.
In a preferred embodiment, in step (1), the mixing is carried out in a VC mixer.
In a preferred embodiment, in step (2), the mixing is carried out in a high-speed mixer.
In a preferred embodiment, in step (2), the atmosphere of the calcination is air.
In a preferred embodiment, in steps (1) and (2), the calcination is carried out in a muffle furnace.
In the invention, the chemical formula of the prepared single crystal nickel cobalt lithium manganate ternary material is Lia(Ni0.5-xCo0.2-yMn0.3- zMb)O2(1.0 ≦ a ≦ 1.10, x + y + z ≦ B, 0.0001 ≦ B ≦ 0.005), the M is one or more elements selected from Zr, Ti, Mg, Al, and B, the x is the number of sites of the nickel element occupied by the doping element M, the y is the number of sites of the cobalt element occupied by the doping element M, and the z is the number of sites of the manganese element occupied by the doping element M.
In the invention, the aggregate structure seed crystal is added, the formation of new crystal nucleus in the solid phase sintering process can be replaced in the sintering process, the added seed crystal is used as the crystal nucleus of the growth environment, the crystal nucleus grows, the crystal can quickly reach the corresponding granularity, the production period of the ternary material is greatly shortened, and the production efficiency is improved. The aggregate structure seed crystal has more crystal boundaries, is beneficial to the diffusion of lithium ions, and can promote the obtaining of a single crystal material with better performance. In the seed crystal stage, the doping elements are diffused into the bulk phase structure of the nickel cobalt lithium manganate, so that the sintered ternary material has a more stable structure and better electrochemical performance.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto. The ternary 523 single crystal precursor used in the examples and comparative examples was purchased from zhongwei new materials, product model HZN 504.
Example 1
(1) Mixing the ternary 523 single-crystal precursor, lithium carbonate and nano flux zirconia by using a VC mixer until the materials are completely mixed, then putting the materials into a muffle furnace for calcination, and heating to 700 ℃ at a heating rate of 3 ℃/min under the air atmosphere for calcination for 20h to obtain aggregate structure crystal seeds with the D50 size of 8.68 mu m; wherein the mass ratio of the lithium source to the precursor is 0.5:1, and the weight of the doping element (zirconium element) in the nano fluxing agent is 0.2 percent of the weight of the ternary 523 single crystal precursor;
(2) adding the aggregate structure seed crystal obtained in the step (1), the ternary 523 single crystal precursor and lithium carbonate into a high-speed mixer for mixing to obtain a mixture, then putting the mixture into a muffle furnace, heating to 700 ℃ at a heating rate of 3 ℃/min in the air atmosphere for calcining for 3h, and continuing heating to 940 ℃ at a heating rate of 3 ℃/min for calcining for 8h to obtain a single-crystal lithium nickel cobalt manganese oxide ternary material Li1.079(Ni0.4998Co0.1999Mn0.2998Zr0.0005)O2(ii) a Wherein the ratio of the amount of lithium in the lithium carbonate to the total amount of nickel, cobalt and manganese in the ternary 523 single crystal precursor is 1.02: 1; the mixture contains 20 wt% of agglomerate structure seeds.
Example 2
(1) Mixing the ternary 523 single-crystal precursor, lithium carbonate and nano-flux titanium oxide by using a VC mixer until the materials are completely mixed, then putting the materials into a muffle furnace for calcination, and heating to 750 ℃ at a heating rate of 3 ℃/min under an air atmosphere for calcination for 18h to obtain aggregate structure crystal seeds with the diameter of 7.92 mu m of D50; wherein the mass ratio of the lithium source to the precursor is 0.7:1, and the weight of the doping element (titanium element) in the nano fluxing agent is 0.1 percent of the weight of the ternary 523 single crystal precursor;
(2) adding the aggregate structure seed crystal obtained in the step (1), the ternary 523 single crystal precursor and lithium carbonate into a high-speed mixer for mixing to obtain a mixture, then putting the mixture into a muffle furnace, heating to 750 ℃ at a heating rate of 2 ℃/min in the air atmosphere for calcining for 3h, and continuously heating to 920 ℃ at a heating rate of 2 ℃/min for calcining for 10h to obtain a single-crystal lithium nickel cobalt manganese oxide ternary material Li1.096(Ni0.4998Co0.1999Mn0.2999Ti0.0004)O2(ii) a Wherein the ratio of the amount of lithium in the lithium carbonate to the total amount of nickel, cobalt and manganese in the ternary 523 single crystal precursor is 0.95: 1; the mixture contains 15 wt% of agglomerate structure seeds.
Example 3
(1) Mixing the ternary 523 single-crystal precursor, lithium carbonate and nano flux magnesium oxide by using a VC mixer until the materials are completely mixed, then putting the materials into a muffle furnace for calcination, and heating to 750 ℃ at the heating rate of 2 ℃/min under the air atmosphere for calcination for 20 hours to obtain aggregate structure crystal seeds with the D50 of 8.65 mu m; wherein the mass ratio of the lithium source to the precursor is 0.6:1, and the weight of doping elements (magnesium elements) in the nano fluxing agent is 0.2 percent of the weight of the ternary 523 single crystal precursor;
(2) adding the aggregate structure seed crystal obtained in the step (1), the ternary 523 single crystal precursor and lithium carbonate into a high-speed mixer for mixing to obtain a mixture, then putting the mixture into a muffle furnace, heating to 800 ℃ at a heating rate of 4 ℃/min in the air atmosphere for calcining for 3h, and continuously heating to 930 ℃ at a heating rate of 2 ℃/min for calcining for 7h to obtain the single-crystal lithium nickel cobalt manganese oxide ternary material Li1.093(Ni0.4992Co0.1997Mn0.2996Mg0.0015)O2(ii) a Wherein the ratio of the amount of lithium in the lithium carbonate to the total amount of nickel, cobalt and manganese in the ternary 523 single crystal precursor is 1.0: 1; the mixture contains 15 wt% of agglomerate structure seeds.
Example 4
(1) Mixing the ternary 523 single-crystal precursor, lithium carbonate and nano flux alumina by using a VC mixer until the materials are completely mixed, then putting the materials into a muffle furnace for calcination, and heating to 650 ℃ at the heating rate of 4 ℃/min under the air atmosphere for calcination for 24 hours to obtain aggregate structure crystal seeds with the D50 of 8.03 mu m; wherein the mass ratio of the lithium source to the precursor is 0.9:1, and the weight of doping elements (aluminum elements) in the nano fluxing agent is 0.3 percent of the weight of the ternary 523 single crystal precursor;
(2) adding the aggregate structure seed crystal obtained in the step (1), the ternary 523 single crystal precursor and lithium carbonate into a high-speed mixer for mixing to obtain a mixture, then putting the mixture into a muffle furnace, heating to 800 ℃ at a heating rate of 3 ℃/min in the air atmosphere for calcining for 3h, and continuously heating to 930 ℃ at a heating rate of 2 ℃/min for calcining for 8h to obtain a single-crystal lithium nickel cobalt manganese oxide ternary material Li1.058(Ni0.4994Co0.1997Mn0.2996Al0.0013)O2(ii) a Wherein the ratio of the amount of lithium in the lithium carbonate to the total amount of nickel, cobalt and manganese in the ternary 523 single crystal precursor is 0.9: 1; the mixture contains 10 wt% of agglomerate structure seeds.
Comparative example 1
The procedure is as described in example 1, except that no nano-flux is added.
Comparative example 2
The process is carried out as described in example 4, except that in step (2) the mix contains 5% by weight of agglomerate structure seeds.
Comparative example 3
The process is carried out as described in example 1, except that in step (2) the mix contains 25% by weight of agglomerate structure seeds.
Comparative example 4
The process was carried out as described in example 1, except that in step (2), the calcination was carried out by: the temperature is raised to 700 ℃ at the heating rate of 3 ℃/min for calcining for 3h under the air atmosphere, and the temperature is raised to 950 ℃ at the heating rate of 3 ℃/min for calcining for 8 h.
Comparative example 5
The process was carried out as described in example 2, except that in step (2), the calcination was carried out by: the temperature is raised to 750 ℃ at the temperature raising rate of 2 ℃/min for 3h in the air atmosphere, and the temperature is raised to 910 ℃ at the temperature raising rate of 2 ℃/min for 10 h.
Comparative example 6
The process was carried out as described in example 4, except that in step (2), the ratio of the amount of the substance of lithium element in lithium carbonate to the total amount of the three elements of nickel, cobalt and manganese in the ternary 523 single crystal precursor was 1.08: 1.
Test example 1
(1) The agglomerate structure seeds obtained in the examples were characterized by SEM, wherein SEM images of the agglomerate structure seeds obtained in example 1 are shown in fig. 1, SEM images of the agglomerate structure seeds obtained in example 2 are shown in fig. 2, SEM images of the agglomerate structure seeds obtained in example 3 are shown in fig. 3, and SEM images of the agglomerate structure seeds obtained in example 4 are shown in fig. 4. As can be seen from the figure, the crystal seeds prepared by different doping elements have small difference in morphology, and the primary particle size has small difference, which mainly presents the morphology of the aggregate structure. The grain size data of the seed crystal D50 shows that the grain size of the secondary sphere of the seed crystal has certain difference according to different element doping.
(2) The particle size of the agglomerate structure seed crystal obtained in example 1 was characterized using a malvern laser particle sizer (Mastersizer2000) and the results are shown in fig. 5, and the agglomerate structure seed crystal obtained in example 1 was characterized using XRD and the results are shown in fig. 6. It can be seen from the figure that the seed Dmin of the agglomerate structure prepared in example 1 is 0.43 μm, D10 is 3.74 μm, D50 is 8.68 μm, D90 is 19.52 μm, and Dmax is 52.49 μm, and the particle size distribution is characterized by the particle size distribution of the agglomerate material as can be seen from the SEM picture. As can be seen from the XRD diagram, characteristic crystal plane peaks such as a 003 crystal plane peak, a 104 crystal plane peak, an 006/012 cleavage peak, a 018/110 cleavage peak and the like of the agglomerate structure seed crystal are all displayed, so that the agglomerate structure seed crystal preliminarily contains the lithium nickel cobalt manganese oxide alpha-NaFeO2Structural features.
(3) The ternary materials obtained in example and comparative example 1 were characterized using SEM, wherein the SEM images of the ternary material obtained in example 1 are shown in fig. 7, the SEM image of the ternary material obtained in example 2 is shown in fig. 8, the SEM image of the ternary material obtained in example 3 is shown in fig. 9, the SEM image of the ternary material obtained in example 4 is shown in fig. 10, and the SEM image of the ternary material obtained in comparative example 1 is shown in fig. 11. As can be seen from the figure, the ternary single crystal material prepared by the embodiment has smooth and mellow particles and good primary particle size consistency. The ternary single crystal material particles prepared in comparative example 1 are not boiled, the single crystallization degree is not high, and the particles are not round and smooth.
Test example 2
The materials prepared in the examples and the comparative examples are used as active ingredients to prepare working electrodes, and the metal lithium is used as a reference electrode to assemble a CR2025 button cell for electrochemical performance test, wherein the test voltage range is 3.0-4.4V. Specific discharge capacity data at different multiplying rates are shown in table 1, and a comparative graph of the specific discharge capacity of the charging 1C50 circles of the example 1 and the comparative example 1 is shown in fig. 12.
TABLE 1
The results in table 1 show that the specific discharge capacity of 0.1C in the example reaches more than 180mAh/g, the first coulombic efficiency reaches more than 88.3%, the specific discharge capacity of the first cycle of 1C cycle reaches more than 163mAh/g, and the retention rate of the cyclic capacity of 1C50 cycles reaches more than 99.6%, which are all superior to those in the comparative example. As can be seen from FIG. 12, the 1 st cycle specific discharge capacity of 1C cycle of example 1 reaches 163.98mAh/g, the 50 th cycle specific discharge capacity reaches 164.35mAh/g, and the 50 th cycle capacity retention rate reaches 100.2%. The 1C cycle 1-cycle specific discharge capacity of the comparative example 1 reaches 161.82mAh/g, the 50-cycle capacity retention rate reaches 95.9%, and the 1C cycle performance of the example 1 is obviously superior to that of the comparative example 1. The single crystal ternary material prepared by the method has the advantages of high capacity, high first coulombic efficiency and good cycle performance.
Slight climbing phenomenon appeared in the 1C50 cycle of example 1 and example 2, the capacity retention rate exceeds 100%, and Zr4+、Ti4+The high valence state and the bigger ionic radius of Zr and Ti elements are related, on one hand, the elements can stabilize the structure and are beneficial to improving the cycle performance, on the other hand, the ionic radius of the elements is bigger, which causes the diffusion of lithium ions to be blocked, the impedance to be enlarged and the capacity at the initial stage of the cycle not to be well released, so the climbing phenomenon occurs. The specific charge capacity of 0.1C and the specific discharge capacity of 0.1C in example 3 were both high, mainly due to: magnesium doping, shortening of Li-O bonds and strengthening of bond energy lead to a decrease in slab-to-slab thickness l (LiO2), while transition metal M-O bonds become longer and slab thickness S (MO2) increases. The bond-dissociation energy of Mg-O (Δ Hf298 ═ 394kJ · mol-1) is greater than that of Ni-O (Δ Hf298 ═ 391kJ · mol-1), so the introduction of Mg2+ in the host structure will provide greater structural stability. Comparative example 4, electrochemical performance was poor mainly because sintering conditions were not suitable to cause single crystal grain to be fired, structure was greatly damaged, and performance was poor.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The preparation method of the single crystal nickel cobalt lithium manganate ternary material is characterized by comprising the following steps:
(1) mixing a ternary 523 single crystal precursor, a lithium source and a nano fluxing agent containing doping elements, controlling the weight ratio of the lithium source to the ternary 523 single crystal precursor to be (0.5-1):1, and then calcining to obtain an aggregate structure seed crystal with D50 of 6-9 mu m;
(2) mixing the aggregate structure seed crystal obtained in the step (1) with a ternary 523 single crystal precursor and a lithium source to obtain a mixture, and then calcining the mixture to obtain a single crystal nickel cobalt lithium manganate ternary material;
wherein the chemical formula of the ternary 523 single crystal precursor is Ni0.5Co0.2Mn0.3(OH)2；
In the step (1), the doping element is selected from at least one of Zr, Ti, Mg, Al and B; the weight of the doping element is 0.1-0.35% of the weight of the ternary 523 single crystal precursor;
in the step (2), the ratio of the quantity of the substance of the lithium element in the lithium source to the total quantity of the three elements of nickel, cobalt and manganese in the ternary 523 single-crystal precursor is (0.9-1.02): 1; the mixture contains 10-20 wt% of agglomerate structure seed crystal.
2. The method of claim 1, wherein the lithium source is lithium carbonate.
3. The method for preparing a single-crystal lithium nickel cobalt manganese oxide ternary material according to claim 1 or 2, wherein in the step (1), the calcining conditions comprise: the heating rate is 2-5 ℃/min, the calcination temperature is 600-800 ℃, and the calcination time is 18-24 h.
4. The method for preparing the single-crystal nickel cobalt lithium manganate ternary material of claim 3, wherein in the step (1), the calcining atmosphere is air.
5. The method for preparing the single-crystal nickel cobalt lithium manganate ternary material of claim 1 or 2, wherein in step (1), the nano-flux is a mixture of one or more of oxide, fluoride, hydroxide, carbonate and basic carbonate containing doping elements.
6. The method for preparing the single-crystal nickel cobalt lithium manganate ternary material according to claim 1 or 2, characterized in that in step (2), the calcination is specifically performed by: the temperature is raised to 700-800 ℃ at the rate of 1-5 ℃/min for calcining for 2-4h, and the temperature is raised to 920-940 ℃ at the rate of 1-4 ℃/min for calcining for 6-10 h.
7. The method for preparing the single-crystal nickel cobalt lithium manganate ternary material according to claim 1 or 2, characterized in that, in step (1), the mixing is carried out in a VC blender.
8. The method for preparing a single-crystal lithium nickel cobalt manganese oxide ternary material according to claim 1 or 2, wherein in the step (2), the mixing is performed in a high-speed mixer.
9. The method for preparing the single-crystal nickel cobalt lithium manganate ternary material according to claim 1 or 2, characterized in that, in step (2), the calcining atmosphere is air.
10. The method for preparing a single-crystal lithium nickel cobalt manganese oxide ternary material according to claim 1 or 2, wherein in the steps (1) and (2), calcination is performed in a muffle furnace.
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